Optical semiconductor device and method for making the device

ABSTRACT

An optical semiconductor device comprises, on a substrate, a fin of diamond-cubic semiconductor material and, at the base of the fin, a slab of that semiconductor material, in a diamond-hexagonal structure, that extends over the full width of the fin, the slab being configured as an optically active material. This semiconductor material can contain silicon. A method for manufacturing the optical semiconductor device comprises annealing the sidewalls of the fin, thereby inducing a stress gradient along the width of the fin.

INCORPORATION BY REFERENCE TO RELATED APPLICATION

Any and all priority claims identified in the Application Data Sheet, orany correction thereto, are hereby incorporated by reference under 37CFR 1.57. This application is a divisional of U.S. application Ser. No.15/076,427, filed Mar. 21, 2016, which claims the benefit of EuropeanApplication No. EP 15160994.8 filed Mar. 26, 2015. Each of theaforementioned applications is incorporated by reference herein in itsentirety, and each is hereby expressly made a part of thisspecification.

FIELD OF THE DISCLOSURE

The present disclosure generally relates to an optical semiconductordevice and a method for making such optical semiconductor device.

BACKGROUND OF THE DISCLOSURE

Silicon (Si) normally crystallizes in the diamond cubic (dc) structure,which corresponds to the zinc-blende structure with single atom type.The cubic Si has an emission around 1.1 eV corresponding to an indirectband gap with low intensity radiation. Therefore it is not a material ofinterest for optoelectronic applications, but it is mainly used as thesubstrate for microelectronic devices and for solar cells. However,there are at least 13 phases of silicon reported, most of which onlyform under high pressure conditions and are otherwise unstable. Theexistence of Si in different crystal structures with differentelectronic properties could offer the possibility of increasedflexibility in the design of future Si-based devices. Among them,hexagonal silicon with lonsdaleite structure, which corresponds to thewurtzite structure with single atom type, and which is also referred toas diamond-hexagonal (dh) Si, Si IV (A) or 2H Si, attracted lot ofattention during the last decade. In 2002, Raffy et al. predicted in“Properties of hexagonal polytypes of group-IV elements fromfirst-principles calculations” in Phys. Rev. B.66, 075201 (2002) thatfor Si the fundamental energy gap decreases with increasing hexagonalityof the polytype.

SUMMARY OF THE DISCLOSURE

It is an object of embodiments of the present disclosure to provide anoptical semiconductor device compatible with sub-14 nanometersemiconductor technology.

The above objective is accomplished by an optical semiconductor deviceand method for manufacturing a semiconductor device according to thepresent disclosure.

In a first aspect, a method for manufacturing an optical semiconductordevice is disclosed, the method comprising: providing a substratecomprising a layer of diamond-cubic semiconductor material; patterningthe diamond-cubic semiconductor layer to form a fin being sandwichedbetween a first confined space and a second confined space, the firstconfined space adjacent to a first major sidewall of the fin and thesecond confined space adjacent to a second major sidewall of the fin;the first and second confined space comprising an oxide material incontact with the major sidewalls; and, annealing the device therebyforming at the base of the fin and across the full width of the fin aslab of the semiconductor material in a diamond-hexagonal structure.

By annealing the device, a first mechanical stress is induced in thefirst confined space and a second mechanical stress in the secondconfined space, wherein the first mechanical stress is different fromthe second mechanical stress, thereby thus inducing a stress gradientover the (width of the) fin.

The slab of diamond-hexagonal semiconductor material formed during themanufacturing process is an optical active material. During theannealing step of the device, the major sidewalls of the fin areoxidized and the diamond-cubic semiconductor material at the base of thefin is transformed (phase transformation) into diamond-hexagonalsemiconductor material.

It is an advantage of certain embodiments that an optical semiconductordevice is formed which is stable during further processing steps,including steps at high temperature (higher than 1100 degrees Celsius).

It is an advantage of certain embodiments that an optical semiconductordevice is formed using standard semiconductor processing steps.

It is an advantage of certain embodiments an optical semiconductordevice may be embedded in the active region together with othersemiconductor devices. The optical semiconductor device is formed at thebase of the fin, whereas other semiconductor devices, such as logic ormemory devices, are formed at the top of the fin.

According to embodiments the first confined space is smaller than thesecond confined space. Due to the different width of the first and thesecond confined space the stress in the first confined space is largerthan the stress in the second confined space, whereby a stress gradientcan be induced over the fin of the device.

The width of the confined spaces before and after the annealing step isdifferent, more specifically the width of the confined spaces willbecome larger after annealing.

According to embodiments at least one of the first and second confinedspace is confined by the fin and another fin. So the fin is sandwichedbetween two confined spaces. A confined space may be sandwiched inbetween a fin and another fin. The space width of the confined space isthereby determined by the distance between a major sidewall of the finand a major sidewall of the another fin. The width of the fin is definedby the distance between the two confined spaces which is between thefirst major sidewall of the fin and the second major sidewall of thefin. The first and second major sidewall are opposite to each other.

According to embodiments the another fin is patterned (and thus alsoannealed) together with the fin. Thus the fin and the another fin arepatterned simultaneously and are annealed simultaneously.

According to embodiments an array of fins may thus be patterned in thediamond-cubic semiconductor material of the optical semiconductordevice. The array of fins comprises a set of fins parallel to oneanother with a confined space in between each fin. So along the array offins the width in between the fins increases from 8 nm to 16 nm to 24 nmetc.

It is an advantage that a gradual increasing spacing between the finsmay be manufactured using standard lithographic techniques such asdouble patterning lithography or extreme ultraviolet (EUV) lithography.

According to embodiments the width between the fins of the array of finsis different. Otherwise said: the confined spaces between the fins havedifferent width. The spacing between the fins may be graduallyincreasing along the array. The spacing may gradually increase with atleast 8 nm from one fin to the next fin.

According to embodiments the width of the first and/or second confinedspaces is preferably smaller than 50 nm.

It is an advantage of embodiments that in an array of fins a series ofparallel slabs of diamond-hexagonal material may be formedsimultaneously.

According to embodiments, annealing the device comprises oxidizing thefirst and the second major sidewall of the fin. Preferably wet oxidationis used.

The wet oxidation may be at 750 degrees Celsius for 30 minutes. If alower temperature is used, a longer oxidation time is needed. Soalternatively 650 degrees Celsius is also possible but for about 250minutes. Alternatively 700 degrees Celsius is also possible but forabout 90 minutes. The oxidation parameters are selected to grow an oxideof the semiconductor material at the fin sidewalls whereby a stressgradient over the fin is created causing the phase conversion of thesemiconductor material.

Alternatively dry oxidation may be used; however the oxidationparameters will differ from wet oxidation. Dry oxidation is slower thanwet oxidation and thus needs longer time. The oxidation parameters areselected to have an oxide at the first and second major sidewalls of thefin to induce a stress in the device causing the phase transformation ofthe semiconductor material.

It is an advantage of certain embodiments that dc-Si to dh-Si phasetransformation occurs at the bottom of the fin over the full width ofthe fin.

It is an advantage of certain embodiments that dc-Si to dh-Si phasetransformation occurs in a controlled way.

According to embodiments the first confined space may be covered with acapping layer, the capping layer being a diffusion barrier for oxygen. Astress gradient is induced over the fin, i.e. a first stress in thefirst confined space which is different from a second stress in thesecond confined space. This difference in stress (i.e. stress gradient)may be induced by using different widths for the confined spaces.Another possibility is a fin having confined spaces with the same widthat both sides, but further comprising a capping layer on top of one ofthe first or the second confined space.

According to embodiments the capping layer comprises SiN.

According to embodiments the semiconductor material is chosen from Si orSi_(x)Ge_(1-x) with 0<x<1.

A III-V material could also be used as for the fin semiconductormaterial as it may have a comparable phase transformation fromsphalerite to wurtzite phase.

According to embodiments the fin is tapered fin.

According to embodiments the width at the base of the fin is preferablysmaller than 50 nm, more preferably smaller than 25 nm.

According to a second aspect an optical semiconductor device isdisclosed comprising a fin of diamond-cubic semiconductor material on asubstrate and at the base of the fin a slab of the semiconductormaterial in a diamond-hexagonal structure across the full width of thefin. The diamond-hexagonal semiconductor slab is an optically activematerial.

According to embodiments the optical semiconductor device may furthercomprise optical contacts to the slab.

According to embodiments the semiconductor material is Si orSi_(x)Ge_(1-x) with 0<x<1

According to embodiments the fin of the optical semiconductor device issandwiched in between a first and a second confined space, the firstconfined space being smaller than the second confined space.

According to embodiments the fin comprises adjacent to the slab a stepat the side of the first confined space and a bulge at the side of thesecond confined space. The bulge is inclined upwards (and away from thesubstrate) by 15 to 20 degrees.

According to embodiments the slab has a thickness in the range of 2 to50 nm.

According to embodiments the optical semiconductor device comprises anarray of fins of diamond-cubic semiconductor material and wherein atleast two fins of the array of fins have a slab of the semiconductormaterial in a diamond-hexagonal structure across the full width of thefin. The spacing between the fins of the array may gradually increase.

It is an advantage of certain embodiments that the semiconductor opticaldevice and the method for manufacturing the semiconductor optical deviceare compatible with sub-14 nanometer semiconductor technology.

It is an advantage of certain embodiments that the method formanufacturing the semiconductor optical device is compatible withstandard semiconductor process steps and device technology.

It is an advantage of certain embodiments that a semiconductor opticaldevice for optoelectronic application may be integrated easily instandard Si-based device technologies.

It is an advantage of certain embodiments that the semiconductor opticaldevice is stable and the optical active material formed duringmanufacturing is unaffected by subsequent high temperature process stepsincluding implantation anneal, epitaxial growth and metallization step(i.e. temperatures higher than the temperature used during the annealingof the fin to induce a phase transformation).

It is an advantage of certain embodiments that a semiconductor opticaldevice may be formed at well-defined positions.

BRIEF DESCRIPTION OF THE DRAWINGS

All drawings are intended to illustrate some aspects and embodiments ofthe present disclosure. The drawings described are only schematic andare non-limiting.

FIGS. 1A-1D show a schematic overview of processing steps formanufacturing an optical semiconductor device according to embodiments.

FIGS. 2A-2B shows TEM picture of an array of fins manufactured accordingto embodiments. FIG. 3B shows a zoom of left part of four fins shown inFIG. 3A.

FIGS. 3A-3C shows TEM picture of an array of fins manufactured accordingto embodiments. FIG. 3B shows a zoom of right part of four fins shown inFIG. 3A. FIG. 3C shows a zoom of the outer right fin of FIG. 3A.

FIGS. 4A-4D shows TEM picture of an optical semiconductor devicemanufactured according to embodiments.

FIGS. 5A-5D shows TEM picture (FIG. 5A, FIG. 5B) and crystallographicpicture (FIG. 5C, FIG. 5D) of an optical semiconductor device.

FIGS. 6A-6B shows TEM picture of a zoom of the slab from an opticalsemiconductor device according to embodiments.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present disclosure will be described with respect to particularembodiments and with reference to certain drawings but the disclosure isnot limited thereto. The drawings described are only schematic and arenon-limiting. In the drawings, the size of some of the elements may beexaggerated and not drawn on scale for illustrative purposes. Thedimensions and the relative dimensions do not correspond to actualreductions to practice of the disclosure.

Furthermore, the terms first, second and the like in the description,are used for distinguishing between similar elements and not necessarilyfor describing a sequence, either temporally, spatially, in ranking orin any other manner. It is to be understood that the terms so used areinterchangeable under appropriate circumstances and that the embodimentsof the disclosure described herein are capable of operation in othersequences than described or illustrated herein.

Moreover, the terms top, under and the like in the description are usedfor descriptive purposes and not necessarily for describing relativepositions. It is to be understood that the terms so used areinterchangeable under appropriate circumstances and that the embodimentsof the disclosure described herein are capable of operation in otherorientations than described or illustrated herein.

In the description provided herein, numerous specific details are setforth. However, it is understood that embodiments of the disclosure maybe practiced without these specific details. In other instances,well-known methods, structures and techniques have not been shown indetail in order not to obscure an understanding of this description.

The important processing steps for the phase transformation in the baseof the fin according to embodiments are schematically illustrated inFIGS. 1A-1D. Fins 101, 102, 103, 104 are patterned in a diamond-cubicsemiconductor substrate material 100 thereby forming an array 110 of (asan example four) fins (FIG. 1A). Each fin has two major sidewalls 101 a,101 b opposite to each other. Each fin 101, 102, 103, 104 is sandwichedin between two confined spaces 105, 106 more precisely a first confinedspace (left from one major sidewall 101 a) and a second confined space111 b (right from the opposite major sidewall 101 b).

According to embodiments the fins may be tapered. A fin is defined by awidth, a length and a height, wherein the width and the length areparallel to the substrate and the height is perpendicular to thesubstrate. The bottom of base of the fin is part of the fin closest tothe substrate. The top of the fin is at the opposite side of the bottomof the fin. The width at the top of the fin is shorter than the width atthe bottom or base of the fin. The fins may be minimum tapered whichmeans the width remains substantially equal along the height of the fin.So the width at the top and the bottom or base of the fin aresubstantially equal

The distance between the fins 101, 102, 103, 104 is defined as the pitchP. So the width S of the confined spaces 105 is defined by the pitch Pminus the width W of the fin.

According to embodiments the confined spaces may have equal width S.

According to embodiments the confined spaces may have a different widthS1, S2.

The confined spaces 105, 106 may be confined by a neighboring fin. Thismeans that a confined space is confined by a major sidewall of one finand a major sidewall of the neighboring fin. The confined spaces 105,106 may be confined by another confining wall, not forming part of afin. The another confining wall may be for example a semiconductor wallat a distance of the fin.

The confined spaces are filled with an oxide material 107 (FIG. 2B).More specifically the confined spaces are filled with a chemicallydeposited oxide material

Next the patterned fins and confined spaces with oxide are oxidized 108.The oxidation step 108 induces stress in the device (the patterned finsand confined spaces with oxide). The patterned fins and confined spacesare manufactured such that the stress in the confined spaces aside of afin and at the major sidewalls is different. A first stress 109 in afirst confined space 105 at the one major sidewall of the fin 104 a isthus larger than a second mechanical stress 110 in the second confinedspace 106 at the opposite oxidized major sidewall 104 b.

Due to the stress induced by the oxidation process in the system, thefin width W and space width S is changed to a width W′ and space widthS′, which is visible by the shift of the fin compared to its initialposition (dotted line). A slab 111 of diamond-hexagonal semiconductormaterial will be formed at the base of the fin (FIG. 1D). In theschematic example shown in FIG. 1D the change in width and space widthis only visible for the outer fins 101, 104 as only for these fins astress gradient is induced due to the difference in width of the firstand second confined spaces. Between fins 102, 103 there is no stressgradient as the confined spaces on both sides of the fin are equal inwidth and thus the stress at both sides of the fins is equal therebythus not inducing a stress gradient. For equally sized confined spaces(space width is equal) the stress gradient may however be induced byadding a capping layer on one of the confined spaces such that a stressgradient may be induced.

According to embodiments the semiconductor material is Si with a phasetransformation from dc-Si to dh-Si. Another possible semiconductormaterial is Si_(x)Ge_(1-x) with 0<x<1. To induce the phasetransformation of Si_(x)Ge_(1-x) from diamond-cubic to diamond-hexagonala Ge oxidation is needed to create sufficient stress to enable thisphase transformation. Another possible semiconductor material is a III-Vmaterial which easily transforms from sphalerite to wurtzite phase.

A method based on advanced silicon device processing is discussed toform diamond-hexagonal silicon nano-ribbons. With an appropriatetemperature anneal applied to densify the oxide fillings between siliconfins, the lateral outward stress exerted on fins sandwiched between wideand narrow oxide windows can result in a phase transition from diamondcubic to diamond-hexagonal Si at the base of these fins. Thediamond-hexagonal slabs are generally 5-8 nm thick and can extend overthe full width, optionally also over the length of the fins i.e. have anano-ribbon shape along the fins. The hexagonal phase is epitaxial tothe cubic structure with (0110)dh//(001)dc and [0001]dh//[110]dc. Theinterfaces are generally parallel to (001)dc or (115)dc. Although thehexagonal silicon is a metastable phase, once formed it is found to bestable during subsequent high temperature steps even during processsteps up to 1050° C. As diamond-hexagonal silicon has a direct bandgapthat emits light in visible range, the growth method has great potentialfor new generation optoelectronic devices.

Dh-silicon can emit visible light (direct transition at ^(˜)1.5 eV) withabout two orders of magnitude higher efficiency than dc-Si as well asnear-infrared light (indirect band gap at ^(˜)0.8 eV). dh-Si, withP6₃/mmc symmetry, 4 atoms per primitive unit cell and approximatelattice parameter of a=b=0.38 nm and c=0.628 nm. This makes it usefulfor optical applications.

The crucial process steps that lead to the diamond-hexagonal siliconformation are schematically illustrated on FIGS. 1A-1D. After patterningof the fins, such as Si etch of the fin structures, the sidewalls have asmoothly varying profile and the silicon is defect free. The finmorphology is unchanged during the oxide fill step but gets modifiedduring the subsequent wet oxygen anneal. Major change is an outwardshift of the outer fins characterized by an increase of the width of thelast spacing, the formation of a bulge on the outside and of a step onthe silicon at the bottom of the outer spacing. In about 60% of theouter fins this goes together with formation of a hexagonal silicon slabover full or partial width of the fin. Most samples investigated arefurther cured in N₂ at higher temperature and got additional temperaturebudgets during the further processing of the devices. All thesesubsequent steps are found to have no impact on the presence ormorphology of the hexagonal silicon. Hence the key process step thatcauses the phase transition to hexagonal silicon is the wet oxidationwhile the dh-phase is stable during further thermal steps. The wetoxidation simultaneously densifies the deposited oxide and oxidizes thesidewalls of the fins, i.e. the fin width w decreases and the spacing sincreases with same amount. The conversion of Si to SiO₂ results in avolume expansion by a factor 2.2, i.e. t_(ox)=2.2t_(Si) with t_(ox) theoxide thickness and t_(Si) the thickness of the consumed Si. The strainε_(ox) in the oxide can be estimated from this volume expansion as

${ɛ\;{ox}} = \frac{\left( {s^{\prime} - s^{''}} \right)}{s^{\prime}}$

with s′ the physical width of the spacing after the oxidation, i.e.s′=s+2 t_(Si) and s″=s+2 t_(ox) the oxide width that has to fit in thephysical width s′. Based on Hooke's law for uniaxial load it allows tocalculate the stress as σ_(ox)=Eε_(ox) with E the Young's modulus of theoxide. At the given oxidation temperature, it can be assumed that theoxide is not very viscous, i.e. is not pushed upwards out of the trenchand the stress is horizontally exerted on the sidewalls of the fins(FIG. 2C). The fins are slightly tapered after the etch so that theinitial spacing s varies from about 25 nm at the top to 10 nm at thebottom of the fin which leads for the applied oxidation conditions to astress of 19 GPa to 35 GPa respectively. Part of the volume expansionwill be compensated by the densification of the deposited oxide. If halfof the expansion is accommodated by the densification, the stress willbe reduced by nearly a factor two, and is therefore still considerable.For inner/dense fins the stress on both sides is similar. However, forthe outer fins the stress on the inner side of the fin is much largerthan on the outer side where the space to the next structures is inmicrometer range and the estimated stress at that side remains below 1GPa (FIG. 2C). Hence, the phase transformation and outwards shift of theouter fins can be related to the strain/stress from the unbalancedexpansion during the wet oxidation step of the wide and narrow oxidewindows next to the outer fins. Qualitatively this estimate shows thatvery high stress is involved and that it can be expected that thetransformation will be initiated at the bottom where the stress is thelargest. Once the transformation is finished and the fin shifted, thestress in the outer spacing will be released and no further modificationwill occur at the bottom of the fins during further processing steps.Moreover the high temperature N₂ anneal after the oxidation step willallow vertical viscous flow of the oxide so that a general stressreduction occurs.

The bulges and inner steps have similar sizes for all 3 major types ofconfigurations at the bottom of the outer fins. The occurrence ofsimilar fin shifts also without defects and with partial dh-Si slabsindicates that the partial dh-regions are not the nucleation state ofthe full dh-slabs. A transformation of mass from the inner side to theouter side of the fin could occur by dislocation nucleation at innerside, fast glide through the fin width and followed by annihilation ofthe dislocation at the outside. However the bulge should then besituated much higher so that the step to bulge plane would correspond toa (111)_(dc) glide plane. Moreover such mechanism will not lead to dh-Siformation.

Transformation of dc- to dh-Si in indentations experiments is explainedas a stress induced martensitic transformation involving shear at theintersection of the secondary twins which are generally present in highdensity in such indents. In our case, only single stacking faults arepresent at the edges of the dh-regions but never extensive twinning isobserved at the bottom of the fins. Therefore such martensitictransformation mechanism seems less likely to explain the dh-Siformation. A model for direct transition of dc to dh-Si by applicationof high stress on the (110)_(dc) plane involves bond breaking and theformation of new 6 atom rings which after relaxation result in dh-Siwith the (0001)_(dh) plane parallel (110)_(dc). The transformationresults in an 18% volume contraction in the [110]_(dc) direction andequal expansion along [001]_(dc) while no volume change occurs in the[110]_(dc) direction. Such mechanism could explain the presence and sizeof the steps on the inner side of the spacing and the reduced width ofthe dh-Si slab compared to the dc-Si above and below. To explain theshift of the fin also in cases of partial or no dh-Si, a reversetransformation mechanism should occur once the stress is released sothat the dc lattice is recovered. Although dh-Si is generally consideredto be a metastable phase, the observed stability of the dh-Si slabsduring further processing is in contradiction with such reversetransformation. An alternative process that overcomes this problem couldbe a dc- to dh-Si transformation that involves a cycle through severalhigh pressure Si phases as observed in high pressure and indentationexperiments. In such experiments an irreversible transition to β-tin Si(Si II) is observed for pressures above 12 GPa which is in the estimatedpressure range at the bottom of the fins. The high pressure β-tin phaseshows a 30% volume reduction per Si atom compared to dc-Si which canexplain the formation of the step and reduction of the lateral width ofthe final dh-Si slab compared to the Si above and below. Upon unloading,the β-tin phase relaxes through a sequence of Si phases. The phasesequence for slow reduction of the stress involves Si II (tetragonal)→SiXII (rhombohedral)→Si III (bcc)→(Si XIII) and then coexistence of dh-Si(Si IV) and amorphous Si.

At the oxidation temperature used for the densification step of theoxide fill a thin region of amorphous Si confined between thedc-crystalline substrate and fin can easily epitaxially regrow.Therefore following such phase sequence the final state could becoexistence of dc- and dh-Si. The formation of either phase in thetransition region might be favored by the local shape and interfaces ofthe intermediate phases. As these phases are metastable and quicklyanneal out above 300° C., they will not be present anymore after theoxidation step and no direct evidence of this phase sequence is observedin our experiments. Nevertheless, such process can explain the presenceof step/bulge with partial or no hexagonal silicon slab combined withstability of the hexagonal phase during further processing.

Most dh-Si slabs show a change of the interface with the dc silicon frominner to outer side of the fin. Whereas the (001)_(dc)//(0110)_(dh)interface corresponds to the perfect alignment of (110)_(dc) with(0001)_(dh), the (115)_(dc) to (0332)_(dh) interface implies a rotationover 3.5° as experimentally observed. Both interface structures can bemodelled with 5 and 7 atom membered rings without any dangling bonds andshow over a nearly 2 nm distance common lattice positions with only asmall misfit (Table 1). However for the (001)_(dc)//(0110)_(dh)interface the reshuffling of the bonds needs to be spread over 2 atomicplanes resulting in a stepped dc/dh interface which will be less stableover longer distances. Steps at the interface may then result in aswitch to the more easily formed (115)_(dc) interface. Table 1 providesdistances between coincident lattice positions in the dc to dh interfaceand lattice mismatch, calculated with dc:a=0.54282 nm−dh:a=0.3837 nm,c=0.6317 nm.

TABLE 1 Interface Dis- Dis- Ratio Interface dc // dh tance dc nm tancedh nm dh/dc structure (001) // 5/2 1.8951 3 1.9192 0.9874 5 and 7(0-110) [110] [0001] atomic rings in dual plane (115) // ½ 1.9944[01-13] 2.0083 1.0069 5 and 7 (03-32) [552] atomic rings in single planeBoth ½ 0.3838 ⅓ 0.3837 0.9997 interfaces, [1-10] [2-1-10] distance alongfin

The formation of dh-Si requires sufficiently high stress to initiate thephase transformation and therefore does not occur for conditions thatlead to lower stress, e.g. by applying less severe oxidation conditions(lower temperature, shorter oxidation time) or with larger initialspacing. As the dh-Si is situated at the base of the fins, it has nodirect impact on the electronic properties of the devices that areprocessed on top of the fins and which only depend on the upper ^(˜)50nm part of the fins. On the other hand by controlling the oxidationconditions and relative spacings on both sides of the fins, conditionsthat favor the dh-Si formation can be searched. As the position andcrystallographic orientation of the resulting dh-Si are well controlled,this opens possibilities to combine in opto-electronic devices theoptical properties of this phase with advanced FinFET basednano-electronic devices. For example, by gradually increasing thespacing between the fins one could generate a series of parallel dh-Sinano-ribbons which could be used as waveguides in the devices.

EXPERIMENTAL RESULTS

Experiments have been performed. Fins with 45 nm pitch P are etched in(dc-)silicon. A nitride cap acts as hardmask during the Si etch. Thespaces are filled with chemical vapor deposited (CVD) oxide which issubsequently densified by an oxidation step during which step themodification at the bottom of the outer fin happens. The schematicillustrates the edge of a dense group of fins.

The investigated FinFET structures are taken from a range of wafersprocessed up to different end-steps for process and device optimization.After the Si etch of the bulk fin structures the spaces are filled witha CVD oxide (O₃/TEOS). To density this oxide a wet oxidation anneal at750° C. or a combination of wet oxidation anneal and high temperature(1050° C.) inert cure are applied. FIGS. 1A-1D presents a schematicdrawing of the process steps involved relevant to this investigation.Self-aligned dual patterning lithography is used to obtain 14 nm findimensions with fin pitch of 45 nm. The investigated fin structuresconsist of groups of 4 fins and dense (10 or 12) fins with constantpitch as shown in FIG. 2A and FIG. 2B. Due to the etch, the sidewallsare sloped so that the spacing typically varies after etch from 25 nm atthe top to 10 nm at the bottom. The groups of fins are separated bydistances of more than 500 nm (FIG. 2A). The fins have lengths of 250 to2500 nm and heights in the range 100-130 nm.

With Transmission Electron Microscopy (TEM) the fins are studied atdifferent moments during the manufacturing method: after Si etching,after oxide fill and densification and after further processing steps ofthe device up to first level metallization (which is part ofback-end-of-line BEOL processing).

FIGS. 2A-2B show bright field (BF) TEM images of a group of 12 and 4fins after fin patterning (etching of the dc-Si material) (FIG. 2A) andthe group of 4 fins at higher magnification (FIG. 2B). The confinedspaces in between the fins are filled with Spin-on-Carbon (SOC) for theTEM specimen preparation. The nitride/oxide hardmask on the fins is usedfor the fin etching. The fins are well defined with a smooth profile atthe base of their sidewalls. All fins show the nominal 45 nm pitch. Dueto the etch step the outer fins are slightly asymmetric.

The morphology of the outer fins is modified after the oxide fill anddensification as illustrated in FIGS. 3A-3C showing high-angle annulardark field scanning transmission electron microscopy (HAADF STEM)results after oxide fill and annealing (i.e., oxidation step,densification of the oxide in the confined spaces). In the group of 12fins (FIG. 3A) and 4 fins (FIG. 3B) the outer fins are shifted outwards,i.e., the width of the confined spaces increased and steps 121 andbulges 120 are formed as illustrated in the zoom (FIG. 3C). These imagesare taken after further process steps where the nitride cap is removedand the oxide is recessed between the top of the fins. These steps haveno effect on the modifications induced by the oxidation step.

In both dense and 4 fin groups, the outer spacings are enlarged and theouter fins moved outwards compared to the configuration after the etch.The width of the inner fins is slightly reduced by the oxidation but theprofile at the bottom of the fins and the pitch are unchanged. The outerfins appear wider than the inner fins and have a typical bulge 120 atthe outer bottom and a step 121 on the silicon on the inner side. Thedirection from step to bulge is nearly 16° inclined upwards to theoutside of the group of fins, i.e. corresponds to a {115}_(dc) plane.Step 121 and bulge 120 have similar widths and indicate an outward shiftof the fin along this plane.

A zoom at the bottom of the outer fins after oxidation and annealing,shows 4 possible configurations which occur in a ratio 45/15/30/10 inthe over 300 studied FinFET structures: a defect across the full finwidth (FIG. 4A), a partial defect (FIG. 4B), no defect but bulge andstep present with similar dimensions as for the defected cases (FIG.4C), and rarely no defect and no clear bulge or step. The defectsconsist of a slab of material of different phase with a thickness ofabout 5 to 8 nm embedded between dc-Si. The full defects run from thestep to a position below the bulge as shown in FIG. 4A. The width of thedefected region is narrower than the Si below and above (including thestep and bulge respectively). FIG. 4D shows a high angle annular darkfield high resolution scanning transmission electron microscopy (HAADFHR-STEM) image taken at 300 kV. The dumbbell structure which can be seenin the silicon substrate and fin, is also present inside the defect withsimilar brightness of the atomic columns, i.e. same composition, butdifferent structural arrangement of the columns. The partial defects arealways situated next to the step at the inner side of the outer fins asshown in FIG. 3B.

Detailed crystal structure analysis of the slab material is shown inFIG. 5A-5D. The atomically resolved HAADF STEM image along the findirection (FIG. 5A) shows that the defect consists of a singlecrystalline material which is in epitaxial relationship to the dc-Si ofsubstrate and fin. The crystal structure is analyzed from the Fouriertransform (FFT) of the image (FIG. 5B). The crystallographicrelationship between the dc-Si and dh-Si lattices as can be derived fromthe HR-STEM image (FIG. 5A) and the fast Fourier transform (FFT) of theimage (FIG. 5B) is illustrated by the schematic in (FIG. 5A) and theindexing of the spots (FIG. 5B). The bottom image (FIG. 5C) shows a cutparallel with an outer fin with insert at bottom left of the latticerelationship and insert at bottom right presenting the dh-Si slab regionat higher magnification, and the corresponding FFT with indexing of thespots (FIG. 5D).

The sharp bright spots in the FFT pattern (FIG. 5B) are due to the dc-Siof substrate and fin along [110] zone axis. The streaked spots withlower intensity are from the slab material. The spots are doubled andelongated due to a rotation of the lattice in the left and right part ofthe defect. The reflections can be indexed as shown in FIG. 5B asdiamond-hexagonal silicon observed along its [21 10] zone axis. Therelationship between dc-Si and dh-Si can be summarized as(001)_(dc)//(0110)_(dh), [110]_(dc)//[0001]_(dh) and [110]_(dc)//[2110]_(dh), which is the same epitaxial relation as observed fordiamond-hexagonal silicon in indentation structures. The latticeparameters a and c are determined from the FFT pattern as 0.38 nm and0.63 nm respectively with the ratio of c/a=1.65, i.e. very close to theideal value for dh-Si as can be calculated based on the dc-Siparameters. The majority of the analyzed defects shows a steppedconfiguration as on FIG. 5A, i.e. part of the defect at the inner sideof the fins show (001)_(dc) interfaces and next part has slopedinterfaces parallel (115)_(dc). Some defects show additional stepsbetween both kinds of interfaces, while only a few ones are observedthat show almost exclusively the (001)_(dc) interface. The lattice inthe horizontal defect parts is exactly aligned with the above mentionedrelationship, i.e. has (110)_(dc)//(0001)_(dh), while a rotation of^(˜)4° around [21 10]_(dh) is present in the defect regions with(115)_(dc) interface plane. This rotation can be related to thedifferent interface structure between the dc and dh lattices at bothinterfaces.

An atomically resolved HAADF STEM image at the slab area of the samplecut parallel with an outer Si fin is presented in FIG. 5C. The dh-Siribbon is magnified further as insert at the bottom right. In the dc-Siof fin and substrate the typical dumbbell pattern is observed, while inthe defect region clearly the regular hexagonal pattern corresponding tothe dh-Si atomic columns along [0001]_(dh) can be seen. The visibilityof the latter pattern will only be ideal for defect parts that areobserved exactly along the [0001]_(dh) zone axis, and with the interface(001)_(dc)/(0110)_(dh) extending on-edge through the full TEM specimenthickness. In view of the defect dimension and the step configuration,even in a very thin sample, this condition will only rarely befulfilled. Superposition of dc and dh lattices in the viewing directionwill result in vertical streaking of the atomic columns. In the inclineddefect parts with (115)_(dc) interfaces, this streaking will be furtherenhanced by the 4° rotation of the dh lattice. Therefore the clearvisibility of the dh-lattice is limited to smaller areas along thedefect. Observations at different positions along the length of the finshow that the dh-lattice can be recognized in regions with severalhundred nanometer length, i.e. nano-ribbons of dh-Si are present at thebase of the fins. The dh-regions are separated by parts of the fin thatappear as dc-Si, which will correspond to the 3^(rd) (or 4^(th)) kind ofconfiguration as observed in the across fin views, i.e. step/bulgewithout defect. The relationship between dc-Si and dh-Si for theobservation with the fin parallel with the image plane, is presented bythe insert at the bottom left of FIG. 5C and the FFT shown in FIG. 5D.It fully agrees with the epitaxy derived from the cut perpendicular tothe Si fins.

The combined information from both observation directions is fullyconclusive for the dh-Si nature of the defect and excludes thepossibility of presence of inclined twin defects.

FIGS. 6A-B shows HR HAADF STEM images of dh-Si edges. The sample cutperpendicular to a fin with partial defect (FIG. 6A) and the sample cutparallel with the fins (FIG. 6B) show the presence of defects in{111}_(dc) planes at the end of the dh regions. Many partial dh-Siregions show a planar defect at their ends in a {111}_(dc) planedirected towards the silicon substrate (FIG. 6A). The lattice resolutionis not always clear at these defects, but where interpretable theycorrespond to stacking faults. In TEM observation mode these defects areoften strongly electron beam sensitive. Stacking faults bonded by a1/6[112] Shockley partial are also present at the dc/dh transition ofthe fins observed parallel with the image plane (FIG. 6B).

All the TEM samples are prepared by focused ion beam (FIB, FEIHelios450HP) with the in-situ lift-out technique. To protect the samplesurface during the ion milling a Spin-on-Carbon (SOC) layer is depositedon the full wafers or wafer pieces. This cap material fills high aspectratio topography well and weakly planarizes the surface. The region ofinterest is further locally capped in the FIB with electron beam or ionbeam deposited Pt. The major milling is done with 30 kV Ga ion beamwhile the milling progress is controlled with the scanning electronmicroscope. Final milling to minimize the damage layer on the specimensis performed with 5 kV Ga ion beam. The typical TEM specimen thicknessis equal or less than 50 nm. Most samples are prepared across groups of4 and 10 or 12 fins. In addition also TEM specimens are preparedparallel the fins so that only the outer fin of the groups is includedin the TEM specimen.

Investigation by transmission electron microscope is performed with FEITecnai F30 or Titan 60-300 Cube in TEM or STEM imaging mode. The highresolution STEM images are acquired in the double corrected Titan systemwith the high-angle annular dark field (HAADF) detector generally at 120kV, unless specified otherwise. This condition allows high resolutionthat resolves the Si-dumbbells without noticeable beam damage of thespecimens. The images are acquired with a screen current of 0.1-0.2 nA,a convergence angle of 22 mrad and an inner collection angle of 50 mrad.HAADF contrast, also known as Z-contrast, can provide directly not onlythe location of the column of atoms but also information on the localcomposition at atomic scale. However, resolution can be further improvedby using 300 kV.

While the disclosure has been illustrated and described in detail in thedrawings and foregoing description, such illustration and descriptionare to be considered illustrative or exemplary and not restrictive. Thedisclosure is not limited to the disclosed embodiments. Variations tothe disclosed embodiments can be understood and effected by thoseskilled in the art in practicing the claimed disclosure, from a study ofthe drawings, the disclosure and the appended claims.

All references cited herein are incorporated herein by reference intheir entirety. To the extent publications and patents or patentapplications incorporated by reference contradict the disclosurecontained in the specification, the specification is intended tosupersede and/or take precedence over any such contradictory material.

Unless otherwise defined, all terms (including technical and scientificterms) are to be given their ordinary and customary meaning to a personof ordinary skill in the art, and are not to be limited to a special orcustomized meaning unless expressly so defined herein. It should benoted that the use of particular terminology when describing certainfeatures or aspects of the disclosure should not be taken to imply thatthe terminology is being re-defined herein to be restricted to includeany specific characteristics of the features or aspects of thedisclosure with which that terminology is associated. Terms and phrasesused in this application, and variations thereof, especially in theappended claims, unless otherwise expressly stated, should be construedas open ended as opposed to limiting. As examples of the foregoing, theterm ‘including’ should be read to mean ‘including, without limitation,’‘including but not limited to,’ or the like; the term ‘comprising’ asused herein is synonymous with ‘including,’ ‘containing,’ or‘characterized by,’ and is inclusive or open-ended and does not excludeadditional, unrecited elements or method steps; the term ‘having’ shouldbe interpreted as ‘having at least;’ the term ‘includes’ should beinterpreted as ‘includes but is not limited to;’ the term ‘example’ isused to provide exemplary instances of the item in discussion, not anexhaustive or limiting list thereof; adjectives such as ‘known’,‘normal’, ‘standard’, and terms of similar meaning should not beconstrued as limiting the item described to a given time period or to anitem available as of a given time, but instead should be read toencompass known, normal, or standard technologies that may be availableor known now or at any time in the future; and use of terms like‘preferably,’ ‘preferred,’ ‘desired,’ or ‘desirable,’ and words ofsimilar meaning should not be understood as implying that certainfeatures are critical, essential, or even important to the structure orfunction of the invention, but instead as merely intended to highlightalternative or additional features that may or may not be utilized in aparticular embodiment of the invention. Likewise, a group of itemslinked with the conjunction ‘and’ should not be read as requiring thateach and every one of those items be present in the grouping, but rathershould be read as ‘and/or’ unless expressly stated otherwise. Similarly,a group of items linked with the conjunction ‘or’ should not be read asrequiring mutual exclusivity among that group, but rather should be readas ‘and/or’ unless expressly stated otherwise.

Where a range of values is provided, it is understood that the upper andlower limit, and each intervening value between the upper and lowerlimit of the range is encompassed within the embodiments.

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth herein for sakeof clarity. The indefinite article “a” or “an” does not exclude aplurality. A single processor or other unit may fulfill the functions ofseveral items recited in the claims. The mere fact that certain measuresare recited in mutually different dependent claims does not indicatethat a combination of these measures cannot be used to advantage. Anyreference signs in the claims should not be construed as limiting thescope.

It will be further understood by those within the art that if a specificnumber of an introduced claim recitation is intended, such an intentwill be explicitly recited in the claim, and in the absence of suchrecitation no such intent is present. For example, as an aid tounderstanding, the following appended claims may contain usage of theintroductory phrases “at least one” and “one or more” to introduce claimrecitations. However, the use of such phrases should not be construed toimply that the introduction of a claim recitation by the indefinitearticles “a” or “an” limits any particular claim containing suchintroduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (e.g., “a” and/or “an” should typically be interpreted to mean “atleast one” or “one or more”); the same holds true for the use ofdefinite articles used to introduce claim recitations. In addition, evenif a specific number of an introduced claim recitation is explicitlyrecited, those skilled in the art will recognize that such recitationshould typically be interpreted to mean at least the recited number(e.g., the bare recitation of “two recitations,” without othermodifiers, typically means at least two recitations, or two or morerecitations). Furthermore, in those instances where a conventionanalogous to “at least one of A, B, and C, etc.” is used, in generalsuch a construction is intended in the sense one having skill in the artwould understand the convention (e.g., “a system having at least one ofA, B, and C” would include but not be limited to systems that have Aalone, B alone, C alone, A and B together, A and C together, B and Ctogether, and/or A, B, and C together, etc.). In those instances where aconvention analogous to “at least one of A, B, or C, etc.” is used, ingeneral such a construction is intended in the sense one having skill inthe art would understand the convention (e.g., “a system having at leastone of A, B, or C” would include but not be limited to systems that haveA alone, B alone, C alone, A and B together, A and C together, B and Ctogether, and/or A, B, and C together, etc.). It will be furtherunderstood by those within the art that virtually any disjunctive wordand/or phrase presenting two or more alternative terms, whether in thedescription, claims, or drawings, should be understood to contemplatethe possibilities of including one of the terms, either of the terms, orboth terms. For example, the phrase “A or B” will be understood toinclude the possibilities of “A” or “B” or “A and B.”

All numbers expressing quantities of ingredients, reaction conditions,and so forth used in the specification are to be understood as beingmodified in all instances by the term ‘about.’ Accordingly, unlessindicated to the contrary, the numerical parameters set forth herein areapproximations that may vary depending upon the desired propertiessought to be obtained. At the very least, and not as an attempt to limitthe application of the doctrine of equivalents to the scope of anyclaims in any application claiming priority to the present application,each numerical parameter should be construed in light of the number ofsignificant digits and ordinary rounding approaches.

Furthermore, although the foregoing has been described in some detail byway of illustrations and examples for purposes of clarity andunderstanding, it is apparent to those skilled in the art that certainchanges and modifications may be practiced. Therefore, the descriptionand examples should not be construed as limiting the scope of theinvention to the specific embodiments and examples described herein, butrather to also cover all modification and alternatives coming with thetrue scope and spirit of the invention.

What is claimed is:
 1. An optical semiconductor device comprising: a finon a substrate, wherein the fin comprises a semiconductor materialhaving a diamond-cubic structure, wherein the fin is sandwiched inbetween a first confined space and a second confined space, wherein awidth of the first confined space is smaller than a width of the secondconfined space; and a slab of the semiconductor material having adiamond-hexagonal structure, wherein the slab is situated across a fullwidth of the fin at a base of the fin, wherein the slab has a thicknessof from 2 nm to 50 nm.
 2. The optical semiconductor device of claim 1,wherein the semiconductor material is selected from the group consistingof Si and Si_(x)Ge_(1-x) wherein 0<x<1.
 3. The optical semiconductordevice of claim 1, wherein the fin comprises a step at a side of thefirst confined space and a bulge at a side of the second confined space,wherein the step is adjacent to the slab.
 4. The optical semiconductordevice of claim 1, wherein the first confined space is adjacent to afirst major sidewall of the fin and the second confined space isadjacent to a second major sidewall of the fin.
 5. The opticalsemiconductor device of claim 4, wherein the first major sidewall andthe second major sidewall are oxidized.
 6. The optical semiconductordevice of claim 1, wherein at least one of the first confined space andthe second confined space is confined by the fin and another majorsidewall of another fin.
 7. The optical semiconductor device of claim 6,wherein the another fin is patterned together with the fin.
 8. Theoptical semiconductor device of claim 7, comprising an array of fins,wherein a width of the confined spaces between fins gradually increasesalong the array of fins.
 9. The optical semiconductor device of claim 8,wherein a width between each fin increases by at least 8 nm from one finto the next fin in the array of fins.
 10. The optical semiconductordevice of claim 1, wherein a width at the base of the fin is smallerthan 50 nm.
 11. The optical semiconductor device of claim 1, comprisingan array of fins, wherein confined spaces between the fins havedifferent widths.
 12. The optical semiconductor device of claim 1,wherein the semiconductor slab is an optically active material.